JP2010229216A - Fluorescent resin composition, sealing material and luminous material using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a luminescent resin composition excellent in dispersion stability, and to provide a sealing material excellent in reliability and a luminous material excellent in luminescence using the luminescent resin composition. <P>SOLUTION: This luminescent resin composition includes a resin composition and a fluorescent material. The resin composition is obtained by co-hydrolytic condensation of (A) an epoxy resin, and an alkoxysilane compound represented by general formula (1) (wherein n=0-3, R<SP>1</SP>is a hydrogen atom or an organic group, a plurality of R<SP>2</SP>may be the same or different, and represent a hydrogen atom or a 1-8C alkyl group). The alkoxysilane compound includes (B) at least one alkoxysilane compound (wherein n=1-2, R<SP>1</SP>is at least one cyclic ether group) and (C) at least one alkoxysilane compound (wherein n=1-2, R<SP>1</SP>is at least one aryl group); and a mixed index α of (B) and (C) represented by formula (2): α=(αc)/(αb) is 0.001-19 [wherein αb is the content (mol%) of the component (B), and αc is the content (mol%) of the component (C)]. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a fluorescent resin composition, a sealing material using the same, and a phosphorescent material.

  In recent years, the environment-related market has made rapid progress, and along with this, the demand for energy-saving products is increasing. Specific examples include, for example, products using light emitting diodes (LEDs), phosphorescent materials, and the like as alternatives to electric lamps and fluorescent lamps. By using these, power consumption can be significantly reduced.

  The LED can be adjusted to various color tones by a combination of an LED chip and a phosphor described later, and the blending of the phosphor is very useful. In addition, phosphorescent materials containing phosphorescent phosphors can be made to emit light even when there is no power supply at night or during power outages, and are expected to be used in various applications in the future.

  For example, as a material for an LED sealing material, an epoxy resin or a silicone resin blended with a phosphor is often used. In addition, a hybrid type of epoxy resin and silicone resin in which a phosphor is blended has been studied.

  Other hybrid type resins include a resin composition in which an epoxy resin and a pre-condensed silicone resin are mixed (for example, see Patent Documents 1 and 2), an epoxy resin and a methoxysilane condensate are mixed, and a dealcoholization reaction. The resin composition obtained by the above (for example, see Patent Documents 3 and 4), and the resin composition obtained by mixing an epoxy resin and a tetramethoxysilane condensate and hydrolytic condensation (for example, see Patent Documents 5 and 6). ), A resin obtained by hydrolytic condensation of an alkoxysilane compound having an organic group having a cyclic ether group and an alkoxysilane compound having an organic group having an aryl group (see, for example, Patent Document 7), an epoxy resin. Modified phenoxy resin obtained by demethanol reaction with γ-glycidoxypropylmethoxysilane ( In example, see Patent Document 8.) It has been proposed.

JP 2006-241230 A JP 2006-225515 A JP 2005-179401 A JP 2003-246838 A International Publication No. 2005/081024 Pamphlet JP 2007-284621 A JP 2008-120443 A JP 2007-321130 A

  However, a sealing material in which a phosphor is blended with an epoxy resin has a limited field of use because the epoxy resin is inferior in light resistance. This tendency is particularly remarkable for epoxy resins having an aromatic ring such as bisphenol A glycidyl ether. In addition, among epoxies, attempts have been made to use alicyclic epoxy resins that tend to have relatively good light resistance, but there is a problem in practice because the viscosity is low and the phosphor tends to settle.

  In addition, a sealing material in which a phosphor is blended with a silicone resin is excellent in light resistance and heat resistance, but is insufficient in hardness, adhesion, and the like of a cured product. Furthermore, when an epoxy resin is used as the outer layer resin of a bullet-type LED, there is a great difference in the glass transition point (hereinafter referred to as Tg) and the linear expansion coefficient between the silicone resin and the epoxy resin. As a result, the risk of disconnection of the LED increases, which may cause a problem in reliability.

  A hybrid type resin of an epoxy resin and a silicone resin is very expensive for performance and is not well accepted in the market.

  Then, this invention is made | formed in view of the said situation, and it aims at providing the fluorescent resin composition excellent in dispersion stability, the sealing material excellent in reliability using the same, and the luminous material excellent in luminescent property. And

  As a result of intensive studies to solve the above problems, the present inventor has formulated a phosphor into a resin composition obtained by cohydrolysis condensation of an epoxy resin and a specific alkoxysilane compound. The present inventors have found that a fluorescent resin composition excellent in dispersion stability, a cured product thereof, and an LED and a phosphorescent material excellent in light emission property and reliability using the same can be provided.

That is, the present invention is as follows.
[1]
(A) an epoxy resin;
An alkoxysilane compound represented by the following general formula (1):
A resin composition obtained by cohydrolyzing and condensing

(In the formula (1), n = 0 to 3, and R ¹ represents a hydrogen atom or an organic group. The plurality of R ² may be the same or different, and may be a hydrogen atom or a carbon number of 1 to 8. Represents an alkyl group of
The alkoxysilane compound is
(B) n = 1-2, and as R ¹ , at least one alkoxysilane compound having at least one cyclic ether group;
(C) at least one alkoxysilane compound in which n = 1 to 2 and R ¹ has at least one aryl group;
A blending index α of (B) and (C) represented by the following formula (2) is 0.001 to 19, and a resin composition:
A phosphor,
A fluorescent resin composition comprising:
Mixing index α = (αc) / (αb) (2)
(In formula (2), αb: content (mol%) of the component (B), αc: content (mol%) of the component (C)).
[2]
The fluorescent resin composition according to [1], wherein the (A) epoxy resin is a liquid having an epoxy equivalent (WPE) of 100 to 600 g / eq and a viscosity at 25 ° C. of 1000 Pa · s or less.
[3]
The fluorescent resin composition according to [1] or [2], wherein the (A) epoxy resin is a polyfunctional epoxy resin that is a glycidyl etherified product of a polyphenol compound.
[4]
As the alkoxysilane compound,
(D) The fluorescent resin composition according to any one of [1] to [3], further including at least one alkoxysilane compound in which n = 0 in the general formula (1).
[5]
The fluorescent resin composition according to any one of [1] to [4], wherein a mixing index β of the alkoxysilane compound represented by the following formula (3) is 0.01 to 1.4;
Mixing index β = {(β ⁿ² ) / (β ⁿ⁰ + β ⁿ¹ )} (3)
(In formula (3),
β ⁿ² : content (mol%) of the alkoxysilane compound in which n = 2 in the general formula (1),
β ⁿ⁰ : the content (mol%) of the alkoxysilane compound in which n = 0 in the general formula (1),
β ⁿ¹ : content (mol%) of the alkoxysilane compound in which n = 1 in the general formula (1),
Here, 0 ≦ {(β ⁿ⁰ ) / (β ⁿ⁰ + β ⁿ¹ + β ⁿ² )} ≦ 0.1).
[6]
The fluorescent resin composition according to any one of [1] to [5], wherein a mixing index γ of the (A) epoxy resin and the alkoxysilane compound represented by the following formula (4) is 0.02 to 15: object;
Mixing index γ = (γa) / (γs) (4)
(In formula (4),
γa: mass of epoxy resin (g),
γs: mass (g) of alkoxysilane compound in which n = 0 to 2 in the general formula (1).
[7]
The fluorescent resin composition according to any one of [1] to [6], wherein the phosphor is an yttrium aluminate phosphor (YAG: Ce phosphor) activated with cerium.
[8]
The sealing material containing the fluorescent resin composition in any one of [1]-[7].
[9]
A phosphorescent material comprising the phosphor resin composition according to any one of [1] to [8], wherein the phosphor is a phosphorescent phosphor.

  ADVANTAGE OF THE INVENTION According to this invention, the fluorescent resin composition excellent in dispersion stability, the sealing material excellent in reliability using the same, and the luminous material excellent in luminescent property are obtained.

  Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. The present invention is not limited to the following embodiment, and can be implemented with various modifications within the scope of the gist.

The fluorescent resin composition of the present embodiment is
(A) an epoxy resin;
An alkoxysilane compound represented by the following general formula (1):
Is a resin composition obtained by cohydrolysis condensation,

(Where a n = 0 to 3, R ¹ represents a hydrogen atom or an organic group. The plurality of R ² may be the same or different, represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. )
The alkoxysilane compound represented by the general formula (1) is (B) n = 1-2, and R ¹ has at least one cyclic ether group, and (C) n = 1 to 2 and R ¹ having at least one aryl group and at least one alkoxysilane compound, and represented by the following formula (2): (B) and (C) Is a fluorescent resin composition containing a resin composition having a mixing index α of 0.001 to 19 and a phosphor.
Mixing index α = (αc) / (αb) (2)
In the formula (2), αb is the content (mol%) of the component (B), and αc is the content (mol%) of the component (C).

  The present inventors have incorporated a phosphor into a resin composition obtained by cohydrolytic condensation of an epoxy resin and a specific alkoxysilane compound, thereby providing a fluorescent resin composition having excellent dispersion stability, It discovered that the sealing material excellent in the reliability using it, and the luminous material excellent in luminescent property were obtained.

((A) Epoxy resin)
The (A) epoxy resin in the present embodiment refers to a compound having an oxirane ring, usually two or more oxirane rings in the molecule, excluding an alkoxysilane compound and a condensate thereof described later, and satisfying the above requirements. If it is, it will not specifically limit. These may be used alone or in combination.

The epoxy equivalent (WPE) of the epoxy resin is preferably 100 to 600 g / eq, more preferably 100 to 500 g / eq, and still more preferably 100 to 300 g / eq.
Depending on the composition balance with the alkoxysilane compound represented by the general formula (1), when the epoxy equivalent (WPE) is less than 100 g / eq, the storage stability of the resin composition may be lowered, and 600 g / eq. If it exceeds 1, cracks may occur in the LED or phosphorescent material containing the resin composition.
Although the compounding purpose of the resin composition of this embodiment is not specifically limited, When using as a sealing material, it is preferable that the epoxy equivalent of an epoxy resin is 100-300 g / eq.

The epoxy resin is preferably a liquid having a viscosity at 25 ° C. of 1000 Pa · s or less, more preferably 500 Pa · s or less, and still more preferably 100 Pa · s or less.
When the viscosity at 25 ° C. exceeds 1000 Pa · s, the fluidity as a liquid is lost, and the compatibility with the alkoxysilane compound described later tends to deteriorate.
In addition, when the viscosity at 25 ° C. is more than 500 Pa · s and 1000 Pa · s or less (500 Pa · s <viscosity ≦ 1000 Pa · s), it can be used by adjusting the temperature at the time of production, selecting a solvent, etc. Since manufacturing conditions tend to be somewhat limited, it is preferably 500 Pa · s or less.

The type of epoxy resin is not particularly limited, and specific examples include polyfunctional epoxy resins that are glycidyl etherified products of polyphenol compounds, alicyclic epoxy resins, aliphatic epoxy resins, and glycidyl etherified products of polyphenol compounds. Polyfunctional epoxy resin, polyfunctional epoxy resin that is glycidyl etherified product of various novolak resins, nuclear hydride of aromatic epoxy resin, aliphatic epoxy resin, heterocyclic epoxy resin, glycidyl ester epoxy resin, glycidylamine And epoxy resins obtained by glycidylation of halogenated phenols.
Among them, a polyfunctional epoxy resin that is a glycidyl etherified product of a polyphenol compound from the viewpoint that it is readily available and has good physical properties when the intended fluorescent resin composition of the present embodiment is cured. An alicyclic epoxy resin is preferable, and a polyfunctional epoxy resin which is a glycidyl etherified product of a polyphenol compound is more preferable. These epoxy resins may be used alone or in combination.

(Polyfunctional epoxy resin)
The polyfunctional epoxy resin which is a glycidyl etherified product of a polyphenol compound is not particularly limited, and specifically, bisphenol A, bisphenol F, bisphenol S, 4,4′-biphenol, tetramethylbisphenol A, dimethyl Bisphenol A, tetramethyl bisphenol F, dimethyl bisphenol F, tetramethyl bisphenol S, dimethyl bisphenol S, tetramethyl-4,4′-biphenol, dimethyl-4,4′-biphenylphenol, 1- (4-hydroxyphenyl)- 2- [4- (1,1-bis- (4-hydroxyphenyl) ethyl) phenyl] propane, 2,2′-methylene-bis (4-methyl-6-tert-butylphenol), 4,4′-butylidene -Bis (3-methyl-6-tert-butyl) Ruphenol), trishydroxyphenylmethane, resorcinol, hydroquinone, 2,6-di (t-butyl) hydroquinone, pyrogallol, phenols having a diisopropylidene skeleton, 1,1-di (4-hydroxyphenyl) fluorene, etc. Examples thereof include phenols having a fluorene skeleton, polyfunctional epoxy resins which are glycidyl etherified products of polyphenol compounds of phenolized polybutadiene.

Among the above, many of the types that are excellent in transparency and fluidity are commercially available and can be obtained at a low price, and the reliability when the LED is manufactured by blending the fluorescent resin composition of the present embodiment as a target. Therefore, a polyfunctional epoxy resin which is a glycidyl etherified phenol having a bisphenol A skeleton is preferable.
A typical example of a polyfunctional epoxy resin which is a glycidyl etherified product of phenols having a bisphenol skeleton is shown below.

When a polyfunctional epoxy resin that is a glycidyl etherified product of a polyphenol compound is used as the epoxy resin, these repeating units (n in the chemical formula showing the above representative examples) are not particularly limited, but preferably Is less than 50, more preferably 0.001 to 10, and still more preferably 0.01 to 2.
When the repeating unit is less than 0.001, the reactivity with the alkoxysilane compound may be deteriorated, and when it exceeds 50, the fluidity is lowered, which may cause a practical problem. From the viewpoint of the balance between the above-described reactivity and fluidity, the repeating unit is particularly preferably from 0.01 to 2.

(Alicyclic epoxy resin)
The alicyclic epoxy resin is not particularly limited as long as it is an epoxy resin having an alicyclic epoxy group, and examples thereof include an epoxy resin having a cyclohexene oxide group, a tricyclodecene oxide group, a cyclopentene oxide group, and the like. Can be mentioned.
Specific examples of the alicyclic epoxy resin include monofunctional alicyclic epoxy compounds such as 4-vinyl epoxycyclohexane, dioctyl epoxyhexahydrophthalate, and di-2-ethylhexyl epoxyhexahydrophthalate. Examples of the bifunctional alicyclic epoxy compound include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexyloctyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4 -Epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene dioxide, bis (3,4-epoxy-6-methyl) (Cyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3,4-epoxy-6-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethyl Glycol di (3,4-epoxycyclohexylmethyl) ether, ethylenebis (3,4-epoxycyclohexane carboxylate), 1,2,8,9- diepoxylimonene, and the like. Examples of the polyfunctional alicyclic epoxy compound include 1,2-epoxy-4- (2-oxiranyl) cyclohexene adduct of 2,2-bis (hydroxymethyl) -1-butanol. In addition, as the polyfunctional alicyclic epoxy compound, epoxidized butanetetracarboxylic acid tetrakis- (3-cyclohexenylmethyl) modified ε-caprolactone or the like can also be used.
Typical examples of the alicyclic epoxy resin are shown below.

(Aliphatic epoxy resin)
The aliphatic epoxy resin is not particularly limited, and specifically, 1,4-butanediol, 1,6-hexanediol, polyethylene glycol, polypropylene glycol, pentaerythritol, xylylene glycol derivatives, etc. Examples thereof include glycidyl ethers of polyhydric alcohols. Typical examples of the aliphatic epoxy resin are shown below.

(Polyfunctional epoxy resin that is glycidyl etherified product of novolak resin)
The polyfunctional epoxy resin that is a glycidyl etherified product of novolak resin is not particularly limited, and examples thereof include phenol, cresols, ethylphenols, butylphenols, octylphenols, bisphenol A, bisphenol F, bisphenol S, and naphthol. Glycidyl etherification products of various novolac resins such as novolak resins made from various phenols such as phenols, xylylene skeleton-containing phenol novolak resins, dicyclopentadiene skeleton-containing phenol novolak resins, biphenyl skeleton-containing phenol novolak resins, and fluorene skeleton-containing phenol novolak resins. Etc.
A typical example of a polyfunctional epoxy resin which is a glycidyl etherified product of a novolak resin is shown below.

(Nuclear hydride of aromatic epoxy resin)
The nuclear hydride of the aromatic epoxy resin is not particularly limited, and examples thereof include glycidyl etherified products of phenol compounds (bisphenol A, bisphenol F, bisphenol S, 4,4′-biphenol, etc.) or various phenols (phenols). , Cresols, ethylphenols, butylphenols, octylphenols, bisphenol A, bisphenol F, bisphenol S, naphthols, etc.) and hydrides of glycidyl ethers of novolac resins. Can be mentioned.

(Heterocyclic epoxy resin)
The heterocyclic epoxy resin is not particularly limited, and examples thereof include heterocyclic epoxy resins having a heterocyclic ring such as an isocyanuric ring and a hydantoin ring.

(Glycidyl ester epoxy resin)
The glycidyl ester-based epoxy resin is not particularly limited, and examples thereof include epoxy resins composed of carboxylic acids such as hexahydrophthalic acid diglycidyl ester and tetrahydrophthalic acid diglycidyl ester.
The glycidylamine epoxy resin is not particularly limited. For example, an epoxy resin obtained by glycidylating amines such as aniline, toluidine, p-phenylenediamine, m-phenylenediamine, diaminodiphenylmethane derivative, and diaminomethylbenzene derivative. Etc.

(Epoxy resin obtained by glycidylation of halogenated phenols)
Epoxy resins obtained by glycidylation of halogenated phenols are not particularly limited. For example, brominated bisphenol A, brominated bisphenol F, brominated bisphenol S, brominated phenol novolac, brominated cresol novolak, chlorinated Examples thereof include epoxy resins obtained by glycidyl etherification of halogenated phenols such as bisphenol S and chlorinated bisphenol A.
The epoxy resin mentioned above can use a polyol together.
The polyol is not particularly limited as long as it is a compound having two or more hydroxyl groups in the molecule. For example, ethylene glycol, diethylene glycol, propylene glycol, trimethylene glycol, 1,2-hexanediol, 1,6- Examples include hexanediol.

(Alkoxysilane compound)
The alkoxysilane compound in this embodiment shows the silicon compound which has 1-4 alkoxyl groups, and is represented by following General formula (1).

In formula (1), n = 0 to 3, and R ¹ represents a hydrogen atom or an organic group.
Moreover, several R < ² > is the same or different and shows a hydrogen atom or a C1-C8 alkyl group.

R ¹ in the general formula (1) represents a hydrogen atom or an organic group and is not particularly limited. Examples of the organic group include an organic group having a cyclic ether group and an organic group having an aryl group, which will be described later. Examples include an organic group having an alkyl group, a vinyl group, a methacryl group, a mercapto group, and an isocyanate group, and among them, an alkyl group is preferable.
Here, examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a butyl group (n-butyl, i-butyl, t-butyl, sec-butyl), and a pentyl group (n -Pentyl, i-pentyl, neopentyl, etc.), hexyl group (n-hexyl, i-hexyl etc.), heptyl (n-heptyl, i-heptyl etc.), octyl group (n-octyl, i-octyl, t-octyl) Etc.), nonyl (n-nonyl, i-nonyl etc.), decyl group (n-decyl, i-decyl etc.), dodecyl group (n-dodecyl, i-dodecyl etc.), and these are linear or Any of a branched alkyl group may be used.
Among these, an alkyl group having 10 or less carbon atoms is preferable, and a methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, and n-hexyl group are more preferable. In addition, hydrogen atoms or a part or all of the main chain skeleton of these alkyl groups are ether groups, ester groups, carbonyl groups, siloxane groups, halogen atoms such as fluorine, methacryl groups, acrylic groups, mercapto groups, amino groups, It may be substituted with at least one group selected from the group consisting of hydroxyl groups.

Moreover, several R < ² > in the above-mentioned general formula (1) is the same or different, respectively, and shows a hydrogen atom or a C1-C8 alkyl group. R ² is not particularly limited as long as it satisfies the above requirements, but is preferably a methyl group or an ethyl group.

((B) component)
The component (B) of the alkoxysilane compound represented by the general formula (1) is at least one kind in the general formula (1), where n = 1 to 2 and R ¹ has at least one cyclic ether group. This is an alkoxysilane compound.

The cyclic ether group refers to an organic group having an ether in which carbon of a cyclic hydrocarbon is substituted with oxygen, and usually means a cyclic ether group having a 3- to 6-membered ring structure. Among them, a 3-membered or 4-membered cyclic ether group having a large ring strain energy and high reactivity is preferable, and a 3-membered ether group is particularly preferable.
Specific examples of the cyclic ether group include, for example, a glycidoxyalkyl group to which an oxyglycidyl group having 4 or less carbon atoms such as β-glycidoxyethyl, γ-glycidoxypropyl, and γ-glycidoxybutyl is bonded, glycidyl Group, β- (3,4-epoxycyclohexyl) ethyl group, γ- (3,4-epoxycyclohexyl) propyl group, β- (3,4-epoxycycloheptyl) ethyl group, β- (3,4 epoxyepoxycyclohexyl) ) Alkyl substituted with a cycloalkyl group having 5 to 8 carbon atoms having an oxirane group such as propyl group, β- (3,4-epoxycyclohexyl) butyl group, β- (3,4-epoxycyclohexyl) pentyl group Groups and the like.
Among the above, glycidoxy in which an oxyglycidyl group is bonded to a C1-C3 alkyl group such as β-glycidoxyethyl group, γ-glycidoxypropyl group, β- (3,4-epoxycyclohexyl) ethyl group, etc. An alkyl group having 3 or less carbon atoms substituted with a C5-C8 cycloalkyl group having an alkyl group or an oxirane group is preferred.

  Specific examples of the component (B) include, for example, 3-glycidoxypropyl (methyl) dimethoxysilane, 3-glycidoxypropyl (methyl) diethoxysilane, 3-glycidoxypropyl (methyl) dibutoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (methyl) dimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (phenyl) diethoxysilane, 2,3-epoxypropyl (methyl) dimethoxysilane, 2,3 -Epoxypropyl (phenyl) dimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltributoxysilane, 2- (3,4-epoxycyclohexyl) ethyl Trimethoxysilane, 2- (3,4-epoxy Hexyl) ethyl triethoxysilane, 2,3-epoxypropyl trimethoxysilane, 2,3-epoxy propyl triethoxy silane, and the like. These may be used alone or in combination.

((C) component)
The component (C) of the alkoxysilane compound represented by the general formula (1) is n = 1 to 2 in the general formula (1), and R ¹ has at least one aryl group. It is an alkoxysilane compound.

  An aryl group refers to a functional group or substituent derived from an aromatic hydrocarbon (simple aromatic ring or polycyclic aromatic hydrocarbon). The aryl group is not particularly limited as long as it matches this, but in consideration of steric hindrance in the higher order structure, a phenyl group, a benzyl group, and the like are preferable.

  Specific examples of the component (C) include, for example, dimethoxymethylphenylsilane, diethoxymethylphenylsilane, phenyltriethoxysilane, trimethoxy [3- (phenylamino) propyl] silane, dimethoxydiphenylsilane, diphenyldiethoxysilane, phenyl Examples include trimethoxysilane and N-phenyl-3-aminopropyltrimethoxysilane. These may be used alone or in combination.

“(B) at least one alkoxysilane compound having general formula (1) where n = 1 to 2 and R ¹ having at least one cyclic ether group”, and “(C) general formula In (1), n = 1 to 2 and R ¹ has at least one aryl group, and the mixing ratio of “at least one alkoxysilane compound” is a mixing index calculated by the following formula (2): It is represented by α.
Mixing index α = (αc) / (αb) (2)
(In formula (2), αb: content of component (B) (mol%), αc: content of component (C) (mol%)).

  In the present embodiment, the mixing index α is set in the range of 0.001 to 19. When the mixing index α is less than 0.001, the fluidity and storage stability of the resin composition are lowered, and when it exceeds 19, the reliability of the manufactured LED is deteriorated. In particular, when considering use as a sealing material, high reliability is required, so the mixing index α is preferably 0.2 to 5, and more preferably 0.3 to 2.

((D) component)
In addition to the components (A) to (C) described above, the composition according to the present embodiment has n = 0 indicating the number of R ¹ in the general formula (1) as a component (D), that is, (OR ² ) May be further cohydrolyzed and condensed.
Examples of the component (D) include tetramethoxysilane and tetraethoxysilane. These may be used alone or in combination.

(Other alkoxysilane compounds)
The composition in this embodiment may further cohydrolyze and condense the alkoxysilane compound represented by the general formula (1) other than the components (B) to (D) described above. Examples of such compounds include dimethyldimethoxysilane, dimethylethoxysilane, hydroxymethyltrimethylsilane, methoxytrimethylsilane, methyltrimethoxysilane, mercaptomethyltrimethoxysilane, methoxydimethylvinylsilane, trimethoxyvinylsilane, bis (2-chloro Ethoxy) methylsilane, ethoxytrimethylsilane, diethoxymethylsilane, ethyltriethoxysilane, dimethoxymethyl-3,3,3-trifluoropropylsilane, ethoxydimethylvinylsilane, 3-chloropropyldimethoxymethylsilane, chloromethyldiethoxymethylsilane , Methyltris (ethylmethylketoxime) silane, trimethylpropoxysilane, trimethoxyisopropoxysilane, diethoxydi Tilsilane, 3- [dimethoxy (methyl) silyl] propane-1-thiol, trimethoxy (propyl) silane, (3-mercaptopropyl) trimethoxysilane, 3-aminopropyltrimethoxysilane, diethoxymethylvinylsilane, butoxytrimethylsilane, Butyltrimethoxysilane, methyltriethoxysilane, methoxyltriethoxysilane, triethoxyvinylsilane, diethoxydiethylsilane, dimethoxyldipropoxysilane, ethyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane Allyltriethoxysilane, 3-bromopropyltriethoxysilane, 3-allylaminopropyltrimethoxysilane, hexyloxytrimethylsilane, propyltriethoxysilane, Xyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- (triethoxysilyl) propyl isocyanate, 3-ureidopropyltriethoxysilane, Methoxytripropylsilane, dibutoxydimethylsilane, methyltripropoxysilane, methyltriisopropoxysilane, octyloxytrimethylsilane, pentyltriethoxysilane, 3- (2-aminoethylamino) propyltriethoxysilane, hexyltriethoxysilane, Examples include 3-methacryloxypropyltriethoxysilane, octyltriethoxysilane, dodecyloxytrimethylsilane, and diethoxydodecylmethylsilane.
In this embodiment, the mixing ratio of the “alkoxysilane compound where n = 2”, “alkoxysilane compound where n = 1” and “alkoxysilane compound where n = 0” of the alkoxysilane compound is expressed by the following formula ( It is represented by the mixture index β calculated in 3).
Mixing index β = {(β ⁿ² ) / (β ⁿ⁰ + β ⁿ¹ )} (3)
In the above formula (3),
β ⁿ² : content (mol%) of the alkoxysilane compound in which n = 2 in the general formula (1),
β ⁿ⁰ : the content (mol%) of the alkoxysilane compound in which n = 0 in the general formula (1),
β ⁿ¹ : content (mol%) of an alkoxysilane compound in which n = 1 in the general formula (1),
And 0 ≦ {(β ⁿ⁰ ) / (β ⁿ⁰ + β ⁿ¹ + β ⁿ² )} ≦ 0.1.

  In the composition of the present embodiment, the mixing index β is preferably 0.01 to 1.4, more preferably 0.03 to 1.2, and still more preferably 0.05 to 1.0. Depending on the composition, if the mixing index β is less than 0.01, the fluidity of the resin composition may deteriorate, and if it exceeds 1.4, the reliability of the LED may deteriorate.

The mixing ratio of the (A) epoxy resin and the alkoxysilane compound “alkoxysilane compound where n = 0 to 2” in the present embodiment is represented by a mixing index γ calculated by the following formula (4).
Mixing index γ = (γa) / (γs) (4)
In the above formula (4),
γa: mass of epoxy resin (g),
γs: represents the mass (g) of the alkoxysilane compound in which n = 0 to 2 in the general formula (1).

  The mixing index γ is preferably 0.02 to 15, more preferably 0.04 to 7, and still more preferably 0.08 to 5. Depending on the composition, if the mixing index γ is less than 0.02, there may be a problem in reliability when used as a sealing material and luminous properties when used as a phosphorescent material. May get worse.

(Cohydrolysis condensation process)
In the present embodiment, first, the resin composition can be obtained by cohydrolyzing and condensing the above-described (A) epoxy resin and the above-described alkoxysilane compound represented by the formula (1).
The “cohydrolytic condensation” in the present embodiment means a hydrolysis condensation reaction performed in the presence of an epoxy resin, and is clearly distinguished from a reaction in the absence of an epoxy resin.
The “cohydrolytic condensation” in the present embodiment is composed of at least two steps of a reflux step without dehydration and a subsequent dehydration condensation step.

  The above-mentioned “refluxing process without dehydration” is a process in which water and a solvent blended for co-hydrolysis and water and a solvent derived from an alkoxysilane compound generated during the reaction are reacted while returning to the reaction solution. It is. Although the method is not particularly limited, the reaction is usually carried out while attaching a cooling pipe to the upper part of the reaction vessel and refluxing the generated water or solvent.

The above-mentioned “dehydration condensation step” is a step in which the condensation reaction is carried out while removing the blended water and solvent and the water and solvent produced in the above “refluxing step without dehydration”. The method is not particularly limited, but usually the reaction is carried out by distillation under reduced pressure using a rotary evaporator or the like.
The heating temperature during the cohydrolysis condensation reaction is preferably 130 ° C. or lower, more preferably 0 to 120 ° C., and still more preferably 0 to 100 ° C.
If it exceeds 130 ° C., the resin composition may be altered depending on the composition. The reaction time for cohydrolytic condensation is preferably 0.5 to 24 hours, more preferably 1 to 12 hours. If it is less than 0.5 hour, the remaining amount of unreacted substances may increase depending on the composition.
The resin composition of this embodiment may be performed by adding a hydrolysis-condensation catalyst during the co-hydrolysis condensation of the above-described (A) epoxy resin and alkoxysilane compound.

  The hydrolysis condensation catalyst is not particularly limited as long as it promotes a conventionally known hydrolysis condensation reaction. For example, a metal (lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, barium, Strontium, zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony, arsenic, cerium, boron, cadmium, manganese, bismuth, etc., organic metals (lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, barium) Strontium, zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony, arsenic, cerium, boron, cadmium, manganese, bismuth and other organic oxides, organic acid salts, organic halides, alkoxides, etc.), inorganic bases Magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, etc.), organic base (Ammonia, tetramethylammonium hydroxide, etc.). Among the above organic metals, organic tin is preferable.

Organotin refers to those in which at least one organic group is bonded to a tin atom, and examples of the structure include monoorganotin, diorganotin, triorganotin, tetraorganotin, etc. Among them, Diorganotin is preferred.
Examples of the organic tin include tin tetrachloride, monobutyltin trichloride, monobutyltin oxide, monooctyltin trichloride, tetra n-octyltin, tetra n-butyltin, dibutyltin oxide, dibutyltin diacetate, dibutyltin dioctate, dibutyl Tin diversate, dibutyltin dilaurate, dibutyltin oxylaurate, dibutyltin stearate, dibutyltin dioleate, dibutyltin / silicon ethyl reactant, dibutyltin salt and silicate compound, dioctyltin salt and silicate compound, dibutyltin bis ( Acetylacetonate), dibutyltin bis (ethyl malate), dibutyltin bis (butylmalate), dibutyltin bis (2-ethylhexylmalate), dibutyltin bis (benzylmalate), dibutyltin bis Allyl malate), dibutyl tin bis (oleyl malate), dibutyl tin malate, dibutyl tin bis (O-phenylphenoxide), dibutyl tin bis (2-ethylhexyl mercaptoacetate), dibutyl tin bis (2-ethylhexyl mercaptopropionate) , Dibutyltin bis (isononyl 3-mercaptopropionate), dibutyltin bis (isooctylthioglycolate), dibutyltin bis (3-mercaptopropionate), dioctyltin oxide, dioctyltin dilaurate, dioctyltin diacetate, Dioctyltin dioctate, dioctyltin didodecyl mercapto, dioctyltin versatate, dioctyltin distearate, dioctyltin bis (ethyl malate), dioctyltin bis (octylmalate), dioctyl Rutin malate, dioctyltin bis (isooctylthioglycolate), dioctyltin bis (2-ethylhexyl mercaptoacetate), dibutyltin dimethoxide, dibutyltin diethoxide, dibutyltin dibutoxide, dioctyltin dimethoxide, dioctyltin diethoxide, dioctyltin dibutoxide, Examples include tin octylate and tin stearate. Among these, dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, dioctyltin diacetate, dibutyltin dimethoxide, dibutyltin diethoxide, dibutyltin dibutoxide, dioctyltin dimethoxide, dioctyltin diethoxide, dioctyltin dibutoxide are preferred.

  These hydrolytic condensation catalysts may be used alone or in combination. For example, organic acid tin and alkaline organic tin can be used in combination, or after reacting with an organic acid salt such as tin, treatment with an inorganic base is also possible. In this case, the inorganic base is preferably a hydroxide of a polyvalent cation such as magnesium hydroxide, calcium hydroxide, strontium hydroxide or barium hydroxide.

The addition amount of the hydrolysis-condensation catalyst is not particularly limited, but the preferable addition amount can be obtained from the mixing index δ which is a ratio to (OR ² ) in the above general formula (1). Here, the mixing index δ is expressed by the following formula (5).
Mixing index δ = (δe) / (δs) (5)
In formula (5),
δe: addition amount of hydrolytic condensation catalyst (mol number),
δs: Indicates the amount (mol number) of (OR ² ) in the general formula (1).

  The mixing index δ is preferably 0.0005 to 5, more preferably 0.001 to 1, and still more preferably 0.005 to 0.5. Depending on the composition of the resin composition, if the mixing index δ is less than 0.0005, the effect of promoting hydrolysis condensation may be difficult to obtain. If it exceeds 5, the ring opening of the cyclic ether group may be promoted. This is not preferable because it may lead to deterioration in storage stability of the resin composition.

In the step of obtaining the resin composition of the present embodiment by cohydrolysis condensation, the amount of water added is not particularly limited, but the preferred amount added is the ratio to (OR ² ) in the above general formula (1). Can be obtained from the mixing index ε. Here, the mixing index ε is expressed by the following formula (6).
Mixing index ε = (εw) / (εs) (6)
In formula (6),
εw: amount of water added (in mol),
εs: Indicates the amount (mol number) of (OR ² ) in the general formula (1).
The mixing index ε is preferably 0.1 to 5, more preferably 0.2 to 3, and still more preferably 0.3 to 1.5. Depending on the composition of the resin composition, if the mixing index ε is less than 0.1, the hydrolysis reaction may not proceed. If it exceeds 5, the storage stability of the resin composition may be reduced.

  The addition of water in the co-hydrolysis condensation described above is mainly performed by hydrolysis of the alkoxysilane compound, and therefore needs to be performed in the “refluxing process without dehydration”. The timing of the addition is not particularly limited, and may be added first or gradually during the reaction using a feed pump or the like.

  The cohydrolysis condensation reaction of the present embodiment can be performed without a solvent or in a solvent. The solvent is not particularly limited as long as it is an organic solvent that can dissolve an epoxy resin and an alkoxysilane compound and is inactive to these, and for example, an aprotic polar solvent such as tetrahydrofuran or dioxane is preferably used. Can be used. Moreover, since it is easy to obtain, alcohol solvents such as methanol, ethanol, butanol, isopropanol, and n-butanol can be used. However, these promote the ring opening of the epoxy group. May not be suitable for use.

  The amount of the solvent added is preferably 0.01 to 20 times, more preferably 0.02 to 15 times, and more preferably 0.02 to 15 times the total mass of the epoxy resin and alkoxysilane compound subjected to the cohydrolysis condensation reaction. The amount is preferably 0.03 to 10 times. Since the molecular weight of the resin composition of the present embodiment can be controlled by the addition amount of the solvent, a resin composition having an appropriate molecular weight and thus an appropriate viscosity can be obtained by setting the addition amount in the above range. Can do.

  The phosphor of this embodiment is a substance that emits fluorescence, that is, absorbs energy such as an electron beam, X-rays, ultraviolet rays, and an electric field, and emits a part of the absorbed energy with a relatively high efficiency (light emission). The material is not particularly limited as long as it is a material to be used), and can be employed regardless of whether it is inorganic or organic. Of these, inorganic phosphors that generally exhibit excellent light-emitting properties are preferred.

  The size of the inorganic phosphor is not particularly limited, but a powder having a particle size of 1 to several tens of μm is often used. In order to develop the performance of the inorganic phosphor, a compound A called an activator (emission center) introduced into a compound A called a matrix is generally used. : Activator B ”.

In particular, when used as an LED sealing material, it is preferable to use a cerium-activated yttrium aluminate phosphor (YAG: Ce phosphor) for reasons described later, and it is preferable to use a phosphorescent phosphor for a phosphorescent material application. . These may be used alone or in combination of two or more.
A preferable blending amount of the phosphor is, as a mass ratio, resin composition: phosphor = 30: 70 to 95: 5, particularly preferably 50:50 to 80:20 (100 in total). When the blending amount of the phosphor is larger than the resin composition: phosphor = 30: 70, the fluidity as the phosphor resin composition may be deteriorated. When the blending amount is less than 95: 5, the function as the phosphor is not satisfactory. May be sufficient.

  The matrix A and the activator B are not particularly limited, and examples of the matrix A include oxide phosphors and nitride phosphors. Examples of the activator B include rare earth elements such as europium (Eu) and cerium (Ce).

As the above-described oxide phosphor, for example, “YAG: Ce phosphor” in which the base A is yttrium aluminate (Y ₃ Al ₅ O ₁₂ : hereinafter referred to as YAG) and the activator B is cerium (Ce). Well known. When this is irradiated with blue light (around 460 nm), yellow light emission occurs efficiently. In this phosphor, a part of Y of “Y ₃ Al ₅ O ₁₂ ” is replaced with another Gd, Tb, or the like, or a part of Al is replaced with Ga or the like to change the structure of the base A. Therefore, the emission peak position can be shifted to the long wavelength side or the short wavelength side, which is very useful.

That is, the “YAG: Ce phosphor” means that the base A is YAG, or a part of Y is replaced with another Gd, Tb, or the like, or a part of Al is replaced with Ga or the like. If the structure is changed and the activator B is a phosphor of Ce, it is not particularly limited, and specific examples thereof include, for example, “Y ₃ Al ₅ O ₁₂ : Ce ³⁺ ” and “(Y ₃ , Gd _0.9 ) Al ₅ O ₁₂ : Ce ³⁺ ”and the like.
As another example of the oxide phosphor, the base A is strontium barium silicate (Sr, Ba) ₂ SiO ₄ and europium (Eu) is introduced as the activator B, “(Sr, Ba) ₂ SiO ₄ : Eu phosphor ”is known. In this system, the emission color can be adjusted from green to orange by changing the composition ratio of Sr and Ba.
Examples of the nitride phosphor described above include the following.

(1) The α-sialon phosphor matrix A is a crystal in which a metal ion such as Ca, aluminum and oxygen are dissolved in an α-type silicon nitride crystal, and “(M _p (Si, Al) ₁₂ (O, _{N) 16} is represented by "here, M metal ions, p is it shows the amount of solid solution specifically" _{Ca p (Si, Al) 12} (O, N) 16:.. Eu "and the like can be mentioned It is done.

(2) The β-sialon phosphor matrix A is represented by a composition of “Si _6-q AL _q O _q N _{8 -q} ” in which aluminum and oxygen are dissolved in a β-type silicon nitride crystal, q represents the amount of solid solution. Specifically, _{"Si 6-q AL q O q} N 8-q: Eu ", and the like.

(3) CaAlSiN ₃ phosphor The matrix A is a nitride crystal obtained by reacting calcium nitride, aluminum nitride, and silicon nitride at a high temperature of 1800 ° C., and specifically includes “CaAlSiN ₃ : Eu” and the like. .

Specific examples of the inorganic phosphor include, for example, “6MgO.As ₂ O5: Mn ⁴⁺ , Y (PV) O ₄ : Eu”, “CaLa _0.1 Eu ₀ , as those having a red emission color. _.9 Ga ₃ O ₇ ”,“ BaY _0.9 Sm _0.1 Ga ₃ O ₇ ”,“ Ca (Y _0.5 Eu _0.5 ) (Ga _0.5 In _0.5 ) ₃ O ₇ ”, “Y ₃ O ₃ : Eu, YVO ₄ : Eu”, “Y ₂ O ₂ : Eu”, “3.5MgO · 0.5MgF ₂ GeO ₂ : Mn ⁴⁺ ”, “(Y · Cd) BO ₂ : Eu” Etc.

Examples of blue light-emitting colors include “(Ba, Ca, Mg) ₅ (PO ₄ ) ₃ Cl: Eu ²⁺ ”, “(Ba, Mg) ₂ Al ₁₆ O ₂₇ : Eu ²⁺ ”, “ ^{_{Ba 3 MgSi 2 O 8: Eu}} 2+ "," ^{_{BaMg 2 Al 16 O 27: Eu}} 2+ "," _{(Sr, Ca) 10 (PO} 4) 6 C l2: Eu 2+ "," (Sr, _{Ca) 10} ( _{PO 4) 6 C l2 · nB} 2 O 3: Eu 2+ "," _{Sr 10 (PO 4) 6 Cl} 2: Eu 2+ "," _{(Sr, Ba, Ca) 5} (PO 4) 3 Cl: Eu 2+ " , “Sr ₂ P ₂ O ₇ : Eu”, “Sr ₅ (PO ₄ ) ₃ Cl: Eu”, “(Sr, Ca, Ba) ₃ (PO ₄ ) ₆ Cl: Eu”, “SrO · P ₂ O ₅ · _B 2 _{O 5:} Eu "," _(BaCa) 5 (P O ₄ ) ₃ Cl: Eu ”,“ SrLa _0.95 Tm _0.05 Ga ₃ O ₇ ”,“ ZnS: Ag ”,“ GaWO ₄ ”,“ Y ₂ SiO ₆ : Ce ”,“ ZnS: Ag, Ga ” , Cl "," _Ca 2 _B 4 OCl: ^{Eu 2+} "," BaMgAl ₄ O _3: ^{Eu 2+} "," _{(M 1, Eu) 10 (} PO 4) 6 C l2 (M 1 are, Mg, Ca, Sr And at least one element selected from the group consisting of Ba) and the like.

Examples of green light-emitting colors include “Y ₃ Al ₅ O ₁₂ : Ce ³⁺ (YAG)”, “Y ₂ SiO ₅ : Ce ³⁺ , Tb ³⁺ ”, “Sr ₂ Si ₃ O ₈ .2SrCl”. ₂ : Eu ”,“ BaMg ₂ Al ₁₆ O ₂₇ : Eu ²⁺ , Mn ²⁺ ”,“ ZnSiO ₄ : Mn ”,“ Zn ₂ SiO ₄ : Mn ”,“ LaPO ₄ : Tb ”,“ SrAl ₂ O ₄ : Eu ”, “SrLa _0.2 Tb _0.8 Ga ₃ O ₇ ”, “CaY _0.9 Pr _0.1 Ga ₃ O ₇ ”, “ZnGd _0.8 Ho _0.2 Ga ₃ O ₇ ”, “SrLa _0.6 Tb _0.4 Al ₃ O ₇ , ZnS: Cu, Al ”,“ (Zn, Cd) S: Cu, Al ”,“ ZnS: Cu, Au, Al ”,“ Zn ₂ SiO ₄ : Mn ”,“ ZnSiO _4: Mn "," Zn : Ag, Cu "," (Zn · Cd) S: Cu "," ZnS: Cu "," GdOS: Tb, "" LaOS: Tb, "" YSiO _4: Ce · Tb "," ZnGeO _4: Mn " , “GeMgAlO: Tb”, “SrGaS: Eu ²⁺ ”, “ZnS: Cu · Co”, “MgO · nB ₂ O ₃ : Ge, Tb”, “LaOBr: Tb, Tm”, “La ₂ O ₂ S: Tb "and the like.
Further, “YVO ₄ : Dy” having a white emission color, “CaLu _0.5 Dy _0.5 Ga ₃ O ₇ ” having a yellow emission color, and the like are also known.

  Specific examples of the organic phosphor include, for example, 1,4-bis (2-methylstyryl) benzene (Bis-MSB), trans-4,4′-diphenylstilbene (DPS) having a blue emission color. ) And stilbene dyes such as 7-hydroxy-4-methylcoumarin (coumarin 4).

  Examples of those having yellow to green fluorescent colors include Brilliantsulfoflavine FF, Basic yellow HG, SINLOIHI COLOR FZ-5005 (manufactured by SINLOIHI), and the like.

Examples of those having yellow to red fluorescent colors include Eosine, Rhodamine 6G, and Rhodamine B.

In general phosphors, when light, an electron beam, or the like, which is an irradiation excitation source, is cut off, light emission is immediately attenuated and disappears. However, as an exception, there is a phosphor that exhibits afterglow for several seconds to several tens of hours after the excitation source is cut off, and this is called a phosphorescent phosphor. The type is not particularly limited as long as it exhibits this property. Specifically, for example, “CaS: Eu, Tm”, “CaS: Bi”, “CaAl ₂ O ₄ : Eu, Nd "," CaSrS: Bi "," _{Sr 2 MgSi 2 O 7: Eu} , Dy "," _{Sr 4 Al 14 O 25: Eu} , Dy "," SrAl ₂ O _4: Eu, Dy "," SrAl ₂ O ₄ : Eu ”,“ ZnS: Cu ”,“ ZnS: Cu, Co ”,“ Y ₂ O ₂ S: Eu, Mg, Ti ”,“ CaS: Eu, Tm ”, etc. Among them, long afterglow “Sr ₂ MgSi ₂ O ₇ : Eu, Dy”, “Sr ₄ Al ₁₄ O ₂₅ : Eu, Dy”, “SrAl ₂ O ₄ : Eu, Dy”, “SrAl ₂ O ₄ : Eu” are preferable. .

Although the manufacturing method of the fluorescent resin composition of this embodiment is not specifically limited, For example, the method shown to the following (1)-(2) can be illustrated. Moreover, you may add suitably the below-mentioned hardening | curing agent, hardening accelerator, polymerization initiator, additive, etc. at the process of (1) or (2).
(1) The resin composition and the phosphor are agitated, mixed, and dispersed by a mixing device described later while simultaneously or separately heating as necessary.
(2) If necessary, defoaming is performed under reduced pressure.
Although the said mixing apparatus is not specifically limited, For example, a raikai machine, a 3 roll mill, a ball mill, a planetary mixer, a line mixer, a homogenizer, a homodisper etc. are mentioned.
The fluorescent resin composition obtained in the present embodiment may further contain a predetermined (F) curing agent and (G) curing accelerator.

  (F) The curing agent and (G) the curing accelerator will be described below.

(Curing agent)
A hardening | curing agent is a substance used in order to harden a resin composition, and is not specifically limited.
As the cured product, for example, acid anhydride compounds, amine compounds, amide compounds, phenol compounds, and the like can be used, and in particular, aromatic acid anhydrides, cyclic aliphatic acid anhydrides, aliphatic acid anhydrides, and the like. An acid anhydride compound is preferable, and a carboxylic acid anhydride is more preferable.
The acid anhydride compounds include alicyclic acid anhydrides, and among the carboxylic acid anhydrides, alicyclic carboxylic acid anhydrides are preferred. These curing agents may be used alone or in combination of two or more.

Specific examples of the curing agent include phthalic anhydride, succinic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride. , Methylhexahydrophthalic anhydride, diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, tetraethylenepentamine, dimethylbenzylamine, ketimine compound, linolenic acid dimer and ethylenediamine Polyamide resin, bisphenols, phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc. Biphenols such as polycondensates of aldehydes with various aldehydes, polymers of phenols with various diene compounds, polycondensates of phenols with aromatic dimethylol, or condensates of bismethoxymethylbiphenyl with naphthols or phenols And modified products thereof, imidazole, boron trifluoride-amine complex, guanidine derivatives and the like.
Specific examples of the alicyclic carboxylic acid anhydride include 1,2,3,6-tetrahydrophthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, hexahydrophthalic anhydride, “4-methylhexahydro Phthalic anhydride / hexahydrophthalic anhydride = 70/30 ”, 4-methylhexahydrophthalic anhydride,“ methylbicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride / bicyclo [2.2. 1] heptane-2,3-dicarboxylic anhydride "and the like.
The addition amount of the curing agent is determined from the mixed index ζ which is a ratio to the cyclic ether group contained in the above-described epoxy resin and alkoxysilane compound.

The mixing index ζ is expressed by the following formula (7).
Mixing index ζ = (ζf) / (ζk) (7)
In formula (7),
ζf: addition amount (number of moles) of curing agent,
ζk: Indicates the amount (mol number) of cyclic ether groups contained in the epoxy resin and the alkoxysilane compound.

  The mixing index ζ is preferably 0.1 to 1.5, more preferably 0.2 to 1.3, and still more preferably 0.3 to 1.5. If the mixing index ζ is less than 0.1, the curing rate may decrease, and if it exceeds 1.5, the moisture resistance as a cured product may deteriorate.

(Curing accelerator)
A curing accelerator is a curing catalyst used for the purpose of promoting the curing reaction.
As the curing accelerator, tertiary amines and salts thereof are preferable.
Specific examples of the curing accelerator include the following (1) to (8).
(1) Tertiary amines: benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, cyclohexyldimethylamine, triethanolamine and the like.
(2) Imidazoles: 2-methylimidazole, 2-n-heptylimidazole, 2-n-undecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1 -Benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1- (2-cyanoethyl) -2-methylimidazole, 1- (2-cyanoethyl) -2-n-un Decylimidazole, 1- (2-cyanoethyl) -2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl -4,5-di (hydroxymethyl) imidazole, 1- (2- Anoethyl) -2-phenyl-4,5-di [(2′-cyanoethoxy) methyl] imidazole, 1- (2-cyanoethyl) -2-n-undecylimidazolium trimellitate, 1- (2-cyanoethyl) ) -2-Phenylimidazolium trimellitate, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazolium trimellitate, 2,4-diamino-6- [2′-methylimidazolyl- (1 ′) )] Ethyl-s-triazine, 2,4-diamino-6- (2'-n-undecylimidazolyl) ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methyl Imidazolyl- (1 ′)] ethyl-s-triazine, isocyanuric acid adduct of 2-methylimidazole, isocyanuric acid adduct of 2-phenylimidazole, 2,4-dia Roh-6- [2'-methylimidazolyl- - (1 ';)] isocyanuric acid adduct of ethyl -s- triazine.
(3) Organophosphorus compounds: diphenylphosphine, triphenylphosphine, triphenyl phosphite and the like.
(4) Quaternary phosphonium salts: benzyltriphenylphosphonium chloride, tetra-n-butylphosphonium bromide, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, n-butyltriphenylphosphine Phonium bromide, tetraphenylphosphonium bromide, ethyltriphenylphosphonium iodide, ethyltriphenylphosphonium acetate, tetra-n-butylphosphonium o, o-diethylphosphorodithionate, tetra-n- Butylphosphonium benzotriazolate, tetra-n-butylphosphonium tetrafluoroborate, tetra-n-butylphosphonium tetraphenylborate, tetraphenylphenol Scan follower tetra Tsu tetraphenylborate and the like.
(5) Diazabicycloalkenes: 1,8-diazabicyclo [5.4.0] undecene-7 and organic acid salts thereof.
(6) Organometallic compounds: zinc octylate, tin actylate, aluminum acetylacetone complex, and the like.
(7) Quaternary ammonium salts: tetraethylammonium bromide, tetra-n-butylammonium bromide and the like.
(8) Metal halide compounds: Boron compounds such as boron trifluoride and triphenyl borate; zinc chloride, stannic chloride and the like.

  The addition amount of a hardening accelerator is calculated | required from the following mixing parameter | index (eta) which is a ratio with respect to the mass of the above-mentioned epoxy resin and alkoxysilane compound.

The mixing index η is represented by the following formula (8).
Mixing index η = (ηg) / (ηk) × 100 (8)
In formula (8),
ηg: mass (g) of curing accelerator,
ηk: mass (g) of epoxy resin and alkoxysilane compound.

  The mixing index η is preferably 0.01 to 5, more preferably 0.05 to 3, and further preferably 0.1 to 1. If the mixing index η is less than 0.01, curing may not proceed well, and if it exceeds 5, the LED may be colored.

Curing of the present embodiment refers to a cured product obtained by irradiating the fluorescent resin composition obtained by the above-described manufacturing method of the present embodiment with heat or energy rays to cause three-dimensional cross-linking between molecules. As the method, thermosetting is particularly preferable.
First, thermosetting will be described.
Thermal curing is a method of obtaining a cured product by causing a chemical reaction by heat and generating three-dimensional cross-linking between molecules.
Examples of the thermosetting method include a method in which the above-mentioned curing agent and curing accelerator are contained in the fluorescent resin composition and heat-treated, and a method in which thermosetting is performed using a thermal cationic polymerization initiator. . In particular, a method of heat-treating a curing agent or a curing accelerator in advance is preferable.

(Thermal cationic polymerization initiator)
The thermal cationic polymerization initiator is a compound that initiates polymerization by generating cationic species by heat. Examples thereof include various onium salts such as quaternary ammonium salts, sulfonium salts, phosphonium salts, and aromatic onium salts. These may be used alone or in combination of two or more. Although the usage method is not particularly limited, a method in which a thermal cationic polymerization initiator is contained in the resin composition and this is heat-treated is general.

  Examples of the quaternary ammonium salt include tetrabutylammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphate, tetrabutylammonium hydrogen sulfate, tetraethylammonium tetrafluoroborate, tetraethylammonium-p-toluenesulfonate, N, N-dimethyl. -N-benzylanilinium hexafluoroantimonate, N, N-dimethyl-N-benzylanilinium tetrafluoroborate, N, N-dimethyl-N-benzylpyridinium hexafluoroantimonate, N, N-diethyl-N-benzyl Trifluoromethanesulfonate, N, N-dimethyl-N- (4-methoxybenzyl) pyridinium hexafluoroantimonate, N, N-diethyl N-(4-methoxybenzyl) preparative Luigi hexafluoroantimonate and the like.

  Examples of the sulfonium salt include triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluoroarsinate, tris (4-methoxyphenyl) sulfonium hexafluoroarsinate, diphenyl (4-phenylthiophenyl). ) Sulfonium hexafluoroarsinate and the like.

Examples of the phosphonium salt include ethyltriphenylphosphonium hexafluoroantimonate and tetrabutylphosphonium hexafluoroantimonate.
As specific examples of the aromatic onium salt, compounds exemplified in Japanese Patent Publication No. 52-14277, Japanese Patent Publication No. 52-14278, Japanese Patent Publication No. 52-14279, and the like can be used.

Next, energy beam curing will be described.
The energy ray curing means a cured product by irradiating the resin composition of the present embodiment with predetermined energy rays (in addition to light such as ultraviolet rays, near ultraviolet rays, visible light, near infrared rays, and infrared rays, electron beams, etc.). Is the way to get.
As the energy ray, light is preferable, and ultraviolet light is more preferable.

Sources of energy rays include, for example, low pressure mercury lamp, medium pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, UV lamp, xenon lamp, carbon arc lamp, metal halide lamp, fluorescent lamp, tungsten lamp, argon ion laser, helium cadmium laser. And various light sources such as a helium neon laser, a krypton ion laser, various semiconductor lasers, a YAG laser, an excimer laser, a light emitting diode, a CRT light source, a plasma light source, and an electron beam irradiator.
In the energy ray curing step, the polymerization initiator added to the resin composition is decomposed by energy ray stimulation to generate a polymerization initiating species, the polymerizable functional group of the target substance is polymerized, and curing proceeds.

The polymerization initiators can be roughly classified into the following three (1) to (3) depending on the active species generated.
These polymerization initiators may be used alone or in combination of two or more.
(1) Those that generate radicals upon irradiation with energy rays.
(2) Those that generate cations by irradiation with energy rays (when the energy rays are light, they are called photoacid generators).
(3) Those that generate anions upon irradiation with energy rays (referred to as photobase generators when the energy rays are light).

  Examples of polymerization initiators used for energy ray curing include benzoins and benzoin alkyl ethers (benzoin, benzyl, benzoin methyl ether, benzoin isopropyl ether, etc.), and acetophenones (acetophenone, 2,2-dimethoxy-2-phenyl). Acetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4- (methylthio) phenyl) -2-monoforino-propane-1- ON, N, N-dimethylaminoacetophenone, etc.), anthraquinones (2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylan Laquinone, 2-aminoanthraquinone, etc.), thioxanthones (2,4-dimethylthiosantone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, etc.), ketals (acetophenone dimethyl ketal, benzyldimethyl) Ketones, etc.), benzophenones (benzophenone, methylbenzophenone, 4,4′-dichlorobenzophenone, 4,4′-bisdiethylaminobenzophenone, etc.), xanthones, benzoates (ethyl 4-dimethylaminobenzoate, 2- (dimethyl) Amino) ethyl benzoate, etc.), amines (triethylamine, triethanolamine, etc.), iodonium salt compounds, sulfonium salt compounds, ammonium salt compounds, phosphonium salt compounds, al Salt compounds, stibonium salt compound, an oxonium salt compound, a selenonium salt compound, a stannonium salt compound and the like.

(Fluorescent resin composition additive)
In the fluorescent resin composition of the present embodiment, various organic resins, inorganic fillers, colorants, leveling agents, lubricants, surfactants, silicone compounds, reactions, as long as their functions are not impaired. Reactive diluents, non-reactive diluents, antioxidants, light stabilizers and the like can be added as appropriate. In addition, plasticizers, flame retardants, stabilizers, antistatic agents, impact resistance enhancers, foaming agents, antibacterial / antifungal agents, conductive fillers, antifogging agents, and crosslinks that are generally used as additives for resins An agent or the like can be blended.

  The organic resin is not particularly limited, and examples thereof include an epoxy resin, an acrylic resin, a polyester resin, and a polyimide resin. In particular, those having highly reactive organic groups such as epoxy resins are preferred.

  Examples of inorganic fillers include silicas (melted crushed silica, crystal crushed silica, spherical silica, fumed silica, colloidal silica, precipitated silica, etc.) silicon carbide, silicon nitride, boron nitride, calcium carbonate, magnesium carbonate, sulfuric acid Barium, calcium sulfate, mica, talc, clay, aluminum oxide, magnesium oxide, zirconium oxide, aluminum hydroxide, magnesium hydroxide, calcium silicate, aluminum silicate, lithium aluminum silicate, zirconium silicate, barium titanate, glass fiber, carbon fiber And molybdenum disulfide. In particular, silicas, calcium carbonate, aluminum oxide, aluminum hydroxide, calcium silicate and the like are preferable, and silicas are more preferable in consideration of physical properties of the cured product. These inorganic fillers may be used alone or in combination of two or more.

  The colorant is not particularly limited as long as it is a substance used for coloring purposes. For example, phthalocyanine, azo, disazo, quinacridone, anthraquinone, flavantron, perinone, perylene, dioxazine, condensed azo, azomethine series Inorganic pigments such as titanium oxide, lead sulfate, chromium yellow, zinc yellow, chromium vermillion, valve shell, cobalt purple, bitumen, ultramarine, carbon black, chromium green, chromium oxide, cobalt green, and the like. These colorants may be used alone or in combination of two or more.

  The leveling agent is not particularly limited, and examples thereof include oligomers having a molecular weight of 4000 to 12000 made of acrylates such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, epoxidized soybean fatty acid, epoxidized abiethyl alcohol, Examples include hydrogenated castor oil and titanium-based coupling agents. These leveling agents may be used alone or in combination of two or more.

  The lubricant is not particularly limited, and examples thereof include hydrocarbon lubricants such as paraffin wax, microwax, and polyethylene wax, and higher fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, and behenic acid. Lubricants, stearylamide, palmitylamide, oleylamide, higher fatty acid amide lubricants such as methylene bisstearamide, hardened castor oil, butyl stearate, ethylene glycol monostearate, pentaerythritol (mono- , Di-, tri-, or tetra-) stearate and other higher fatty acid ester lubricants, cetyl alcohol, stearyl alcohol, polyethylene glycol, polyglycerol and other alcohol lubricants, lauric acid, myristic acid, palmitic Natural waxes such as metal soaps such as magnesium, calcium, cadmium, barium, zinc, lead, etc., such as acid, stearic acid, arachidic acid, behenic acid, ricinoleic acid, naphthenic acid, carnauba wax, candelilla wax, beeswax, montan wax And the like. These lubricants may be used alone or in combination of two or more.

  The surfactant is an amphiphilic substance having a hydrophobic group having no affinity for the solvent in the molecule and an amphiphilic group (usually a hydrophilic group) having an affinity for the solvent. The type of the surfactant is not particularly limited, and examples thereof include silicone surfactants and fluorine surfactants. Surfactants may be used alone or in combination of two or more.

  The silicone compound is not particularly limited, and examples thereof include silicone resin, silicone condensate, silicone partial condensate, silicone oil, silane coupling agent, silicone oil, polysiloxane and the like. These may be modified by introducing organic groups into both ends, one end, or side chains. The modification method is not particularly limited. For example, amino modification, epoxy modification, alicyclic epoxy modification, carbinol modification, methacryl modification, polyether modification, mercapto modification, carboxyl modification, phenol modification, silanol modification, Examples include polyether modification, polyether / methoxy modification, and diol modification.

  The reactive diluent is not particularly limited. For example, alkyl glycidyl ether, alkylphenol monoglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, alkanoic acid glycidyl ester, ethylene Examples include glycol diglycidyl ether and propylene glycol diglycidyl ether.

  The non-reactive diluent is not particularly limited, and examples thereof include high boiling point solvents such as benzyl alcohol, butyl diglycol, and propylene glycol monomethyl ether.

  The antioxidant is not particularly limited, and examples thereof include organic phosphorus antioxidants such as triphenyl phosphate and phenylisodecyl phosphite, and organic sulfurs such as distearyl-3,3′-thiodipropinate. Examples of the antioxidant include phenolic antioxidants such as 2,6-di-tert-butyl-p-cresol.

  The light stabilizer is not particularly limited, and examples thereof include benzotriazole-based, benzophenone-based, salicylate-based, cyanoacrylate-based, nickel-based, and triazine-based ultraviolet absorbers, hindered amine-based light stabilizers, and the like.

The following substances may be further added to the fluorescent resin composition and its cured product produced by the production method of the present embodiment.
For example, solvents, oils and fats, processed oils, natural resins, synthetic resins, pigments, dyes, pigments, release agents, preservatives, adhesives, deodorants, flocculants, cleaning agents, deodorants, pH adjusters, photosensitive materials, Ink, electrode, plating solution, catalyst, resin modifier, plasticizer, softener, agrochemical, insecticide, fungicide, pharmaceutical raw material, emulsifier / surfactant, rust inhibitor, metal compound, filler, cosmetic / pharmaceutical raw material , Dehydrating agent, drying agent, antifreeze, adsorbent, colorant, rubber, foaming agent, colorant, abrasive, mold release agent, flocculant, antifoaming agent, curing agent, reducing agent, flux agent, film treatment agent, Casting raw materials, minerals, acids / alkalis, shot agents, antioxidants, surface coating agents, additives, oxidants, explosives, fuels, bleaches, light emitting elements, fragrances, concrete, fibers (carbon fibers, aramid fibers, glass) Fiber), glass, metal, excipient, disintegrant, Mixture, fluidizing agents, gelling agents, stabilizers, preservatives, buffering agents, suspending agents, thickeners, and the like.
When the fluorescent resin composition is used in combination with an LED, its purpose and use site are not particularly limited, but it is suitable for use as a sealing material described later.

An LED using the sealing material of this embodiment is a kind of semiconductor element, and emits light when a current is passed. An LED has two terminals, an anode and a cathode. When a positive voltage is applied to the anode and a negative voltage is applied to the cathode, a current flows at a voltage of several volts and light is emitted. As a light emission principle, an electroluminescence effect (EL effect) is used, and an organic EL is included in the LED in terms of classification.
These LEDs include red, green, orange, blue, and the like. If the three primary colors of light are used, light of various colors including white can be produced by combining these. In addition, when a phosphor is added to the LED, the LED absorbs light emitted from the light-emitting element and performs wavelength conversion, thereby providing an LED having a color tone different from that of the light-emitting element at the site of the sealing material. It becomes possible.
The shape of the LED is not particularly limited and can be appropriately selected according to the application. For example, a bullet type, a surface mount type (hereinafter referred to as SMD type), a Chip On Board type (hereinafter referred to as COB type). , Power LED type, plate shape, thin film shape and the like.
The structure of the LED is not particularly limited, and is composed of a sealing material, an outer layer resin, an LED chip, a lead frame, a bonding wire, and the like.

The above-described sealing material is a member having a function of protecting a predetermined target from factors (foreign substances) such as temperature, moisture, and dust, mainly in an airtight and liquidtight state. Foreign materials include sound, vibration, and erosion by chemical materials.
Moreover, as a use site | part of a sealing material, it is used in many cases, for example for protection of the junction part of a LED chip main body, a LED chip, a wire, and a lead wire. It can also be used in a lead-free reflow mounting process corresponding to the RoHS directive, which is becoming the mainstream instead of the conventional lead solder process.
As the above-mentioned outer layer resin, for example, an epoxy resin, a silicone resin, an epoxy-silicone hybrid resin, or the like is generally used as long as it is a resin of the outer layer portion of the sealing material. However, heat resistance and light resistance are not required as much as the sealing material, and the amount of use is large, so that an epoxy resin is often used for cost reduction.

  The LED chip is an element made of an element such as gallium (Ga), arsenic (As), indium (In), P (phosphorus), N (nitrogen), Al (aluminum), and the like. Light can be emitted in various colors. For example, by combining Ga, As, In, and P, it is possible to emit red to yellow light, and by combining In, Ga, and N, it is possible to emit blue to green light or ultraviolet light. it can. Therefore, in recent years, there is a great demand for InGaN-based devices because there is a high need for blue-based light that can be used as a light source for white LEDs depending on the combination with a phosphor. Specific examples of the material, emission color, and emission wavelength of typical LED chips include, for example, “GaInN (ultraviolet light to blue to green, about 370 to 530 nm)”, “InGaAlP / GaAs (green to yellow-green, about 560). ˜580 nm), “InGaAlP / GaP (yellow, about 590 nm)”, “InGaAlP (red, about 644 nm)”, “GaAlAs / GaAs (red, about 660 nm)”, “GaP / GaP (red, about 700 nm)” , “GaAlAs (infrared light, about 880 nm)”, “GaAs (infrared light, about 940 nm)” and the like.

  The bonding wire is a wire for connecting the electrode of the LED chip and the lead electrode, and the material is not particularly limited as long as it is a conductive material, but usually copper (Cu), gold (Au), aluminum (Al), or a wire made of an alloy thereof. Moreover, the surface may be coat | covered with other electroconductive substances, such as silver (Ag).

  The use of the LED using the fluorescent resin composition of the present embodiment as a sealing material is not particularly limited. For example, “backlight of mobile phone, display part of business phone, key panel, etc.”, optical disc Device heads, “LCD backlights used in large LCDs, small LCDs, televisions, notebook computers, LCD monitors, etc.”, “lighting devices such as flashlights, general lighting, environmental equipment lighting, street lights, indirect lighting”, “instruments” , Brake lamps, rear combination lamps, headlights, downlights, interior lighting, car stereos and other display parts for cars, traffic signal lamps, LED displays for road signs, stations, airports, etc. Board ”,“ outdoor signboards and displays ”,“ medical LEDs used in gastrocameras, endoscopes, etc. ”,“ pachinko machines, game machines ” LED for Amuse instrument equipment of beam machine or the like ", it can be used as such as" copy / facsimile, general display portion of consumer electronics products. "

The light storage of this embodiment is called “light storage” when the light is excited by light stimulation such as sunlight, fluorescent light, ultraviolet light, etc., and energy is converted to emit light, and the light emission that persists even after the stimulation is stopped. On the other hand, light emission only during stimulation is called “fluorescence”.
That is, the phosphorescent material of the present embodiment refers to a material that emits light for a long time while being excited by the light stimulus, converting energy to emit light, and gradually emitting light even after excitation is stopped.
The use of the phosphorescent material of the present embodiment is not particularly limited. For example, indications at night / power outages, disaster prevention / safety signs, clocks, wallpaper, electric switches, signs, clothing, shoes, bicycles / bikes It can be used as a reflector, adhesive tape, fishing gear such as a fishing hook / floating, exercise equipment, accessories, toys and the like.

Although the Example which demonstrated this embodiment concretely is illustrated below, this embodiment is not limited to a following example, unless the summary is exceeded.
The physical properties in Examples and Comparative Examples were evaluated as follows.

<Epoxy equivalent (WPE)>
It was measured according to “JIS K 7236: 2001 (How to determine epoxy equivalent of epoxy resin)”.

<Viscosity>
Measurement was performed under the following conditions.
Rotating E-type viscometer: “TV-22” manufactured by Toki Sangyo Co., Ltd.
Rotor: 3 ° × R14 (Other rotors may be selected as necessary.)
Measurement temperature: 25 ° C
Sample volume: 0.4mL

<Calculation of mixing index α>
The mixing index α was calculated from the following formula (2).
Mixing index α = (αc) / (αb) (2)
here,
αb: (B) In the general formula (1), n = 1 to 2, and R ¹ is an alkoxysilane compound content (mol%) having at least one cyclic ether group,
αc: (C) In general formula (1), n = 1 to 2, and R ¹ represents the content (mol%) of an alkoxysilane compound having at least one aryl group.

<Calculation of mixing index β>
The mixing index β was calculated from the following formula (3).
Mixing index β = {(β ⁿ² ) / (β ⁿ⁰ + β ⁿ¹ )} (3)
here,
β ⁿ² : content (mol%) of the alkoxysilane compound in which n = 2 in the general formula (1),
β ⁿ⁰ : the content (mol%) of the alkoxysilane compound in which n = 0 in the general formula (1),
β ⁿ¹ : content (mol%) of an alkoxysilane compound in which n = 1 in the general formula (1),
At this time, 0 ≦ {(β ⁿ⁰ ) / (β ⁿ⁰ + β ⁿ¹ + β ⁿ² )} ≦ 0.1.

<Calculation of mixing index γ>
The mixing index γ was calculated from the following equation (4).
Mixing index γ = (γa) / (γs) (4)
here,
γa: mass of epoxy resin (g),
γs: Mass (g) of the alkoxysilane compound in which n = 0 to 2 in the general formula (1).

<Calculation of mixing index δ>
The mixing index δ was calculated from the following equation (5).
Mixing index δ = (δe) / (δs) (5)
here,
δe: addition amount of hydrolytic condensation catalyst (mol number),
.delta.s: The amount of the general formula ^{(1) (OR 2) (} mol number), showing the.

<Calculation of mixing index ε>
The mixing index ε was calculated from the following equation (6).
Mixing index ε = (εw) / (εs) (6)
here,
εw: amount of water added (in mol),
εs: Indicates the amount (mol number) of (OR ² ) in the general formula (1).

<Calculation of mixing index ζ>
The mixing index ζ was calculated from the following equation (7).
Mixing index ζ = (ζf) / (ζk) (7)
here,
ζf: addition amount (number of moles) of curing agent,
[zeta] k: The amount (mol number) of cyclic ether groups contained in the epoxy resin and the alkoxysilane compound.

<Calculation of mixing index η>
The mixing index η was calculated from the following formula (8).
Mixing index η = (ηg) / (ηk) × 100 (8)
here,
ηg: mass (g) of curing accelerator,
ηk: mass (g) of epoxy resin and alkoxysilane compound.

<Calculation of storage stability index θ and storage stability of resin composition>
The storage stability in the resin composition was evaluated by a storage stability index θ represented by the following general formula (9).
Storage stability index θ = (storage viscosity) / (starting viscosity) (9)
The container containing the resin composition immediately after production was sealed and the temperature was adjusted at 25 ° C. for 2 hours, and then the viscosity at 25 ° C. was measured, which was defined as “starting viscosity”.
Further, the container containing the resin composition was sealed and stored in a constant temperature incubator at 25 ° C. for 2 weeks. After storage, the viscosity at 25 ° C. was measured, and this was designated as “storage viscosity”.
When the resin composition was fluid (viscosity was 1000 Pa · s or less) and the storage stability index θ was 4 or less, it was judged to have storage stability.

<Dispersion stability test of fluorescent resin composition>
After producing the fluorescent resin composition, it was sealed in a 50 mL glass bottle and stored in a constant temperature incubator at 25 ° C. for 5 hours. After storage, the appearance was observed, and the precipitation and uniformity of the phosphor were visually confirmed. When the phosphor was not precipitated and the phosphor was uniformly dispersed, it was judged that the dispersion stability was acceptable.

<Light resistance test of cured product (cured product of resin composition)>
A cured product in which a solid (phosphor) is dispersed has a large variation in yellowness (YI). Therefore, a cured product was prepared with a resin composition to which no phosphor was added by the following method, and the evaluation result was regarded as light resistance evaluation.
(1) The cured product solution prepared by the method described later was cured to produce a cured product of 20 mm × 10 mm × thickness 3 mm.
(2) The cured product was covered with a black mask of 25 mm × 15 mm × thickness 1.2 mm with a hole having a diameter of 5.5 mm to obtain a sample for light resistance test.
(3) A UV irradiation device (USHIO INC., “Spot Cure SP7-250DB”) is connected to the sample in a constant temperature incubator at 50 ° C. via an optical fiber so that the sample can be irradiated with UV light. Got ready.
(4) The sample was set in a constant temperature incubator at 50 ° C. with the black mask on top.
(5) UV light of 2 W / cm ² was irradiated for 96 hours from the upper part of the black mask so that UV light could be irradiated to a hole having a diameter of 5.5 mm.
(6) The UV-irradiated sample was measured with a spectrocolorimeter (Nippon Denshoku Industries Co., Ltd., “SD5000”) with an integrating sphere opening modified to a diameter of 10 mm.
(7) Yellowness (YI) was determined according to “ASTM D1925-70 (1988): Test Method for Yellowness Index of Plastics”. When this YI was 13 or less, it was judged as passing.
<Light emission test of LED>
The LED was turned on, visually confirmed with the color tone, and when the color tone changed from blue to white with respect to the LED not blended with the phosphor, the light emitting property was regarded as acceptable.

<Luminescence test of phosphorescent material (afterglow time measurement)>
Sample, "JIS Z9107: 2008 Safety labels - Performance Classification, performance criteria and test methods" is defined in the conventional light source fluorescent lamp _{D 65,} it is irradiated at 200 lux for 20 minutes. After irradiation, the afterglow luminance was measured with a luminance meter, and the time until it reached 0.3 mcd / m ² or less was defined as the afterglow time. When the afterglow time was 120 minutes or more, the light emission was judged to be acceptable.

<LED reliability test (1) (continuous operation test: hereinafter referred to as “L test”)>
Ten LEDs are connected to METHOD 1026.5 (STEADY-STATE OPERATION LIFE) of “MIL-STD-750E (TEST METHODS FOR SEMICONDUCTOR DEVICES)” and “MIL-STD-883G (MICROCIRCUITS.5)”. According to (STEADY-STATE LIFE), the following conditions were evaluated.
“IF = 20 mA, Ta = 25 ° C., 960 hours” was turned on, and the total luminous flux (lm) before and after lighting was measured. Further, for each LED, “total luminous flux maintenance factor (%) = (total luminous flux after lighting) / (total luminous flux before lighting) × 100” is obtained, and the minimum value of the total luminous flux maintenance factor (%) of all LEDs is When it was 90% or more, it was judged to be acceptable.

<LED reliability test (2) (thermal shock test: hereinafter referred to as “TS test”)>
Ten LEDs were evaluated under the following conditions in accordance with test method 307 (thermal shock test) of “EIAJ ED-4701 / 300 (Semiconductor device environment and durability test method (strength test I)”).
“-10 ° C. (5 minutes) to 100 ° C. (5 minutes)” was set as one cycle, and after 100 cycles of thermal shock, the lighting of the LEDs was confirmed.
<LED reliability test (3) (temperature cycle test: hereinafter referred to as “TC” test)>
Ten LEDs were evaluated under the following conditions in accordance with test method 105 (temperature cycle test) of “EIAJ ED-4701 / 100 (Semiconductor device environment and durability test method (life test I)”).
“-40 ° C. (30 minutes) to 85 ° C. (5 minutes) to 100 ° C. (30 minutes) to 25 ° C. (5 minutes)” is taken as one cycle. When all 10 pieces were lit, it was judged as passing.
In evaluation of said LED, when all the light resistance and reliability tests (1)-(3) are passing, it was judged that it was a pass as comprehensive judgment.

About the raw material used by the Example and the comparative example, it shows to the following (1)-(10).
(1) Epoxy resin (1-1) Epoxy resin A: Poly (bisphenol A-2-hydroxypropyl ether) (hereinafter referred to as “Bis-A epoxy resin”)
・ Product name: “AER”, manufactured by Asahi Kasei Epoxy Corporation
Moreover, the epoxy equivalent (WPE) and viscosity measured by the above-mentioned method were as follows.
Epoxy equivalent (WPE): 188 g / eq
Viscosity (25 ° C.): 14.8 Pa · s
(1-2) Epoxy resin B: 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexylcarboxylate (hereinafter referred to as “alicyclic epoxy resin”)
・ Product name: “Celoxide 2021P” manufactured by Daicel Chemical Industries, Ltd.
Moreover, the epoxy equivalent (WPE) and viscosity measured by the above-mentioned method were as follows.
Epoxy equivalent (WPE): 131 g / eq
Viscosity (25 ° C.): 227 mPa · s

(2) Alkoxysilane compound (2-1) Alkoxysilane compound H: 3-glycidoxypropyltrimethoxysilane (hereinafter referred to as “GPTMS”)
・ Product name: “KBM-403”, manufactured by Shin-Etsu Chemical Co., Ltd.
(2-2) Alkoxysilane Compound I: Phenyltrimethoxysilane (hereinafter referred to as “PTMS”)
・ Product name: “KBM-103” manufactured by Shin-Etsu Chemical Co., Ltd.
(2-3) Alkoxysilane Compound J: Dimethyldimethoxysilane (hereinafter referred to as “DMDMS”)
・ Product name: “KBM-22” manufactured by Shin-Etsu Chemical Co., Ltd.
(2-4) Alkoxysilane Compound K: Tetraethoxysilane (hereinafter referred to as “TEOS”)
・ Product name: “KBE-04”, manufactured by Shin-Etsu Chemical Co., Ltd.

(3) Solvent: Tetrahydrofuran (Wako Pure Chemical Industries, Ltd., stabilizer-free type) (hereinafter referred to as “THF”)

(4) Hydrolysis condensation catalyst: dibutyltin dilaurate (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter referred to as “DBTDL”)

(5) Curing agent: “4-methylhexahydrophthalic anhydride / hexahydrophthalic anhydride = 70/30”
-Product name: “Rikacid MH-700G” manufactured by Shin Nippon Rika Co., Ltd.

(6) Curing accelerator: amine compound-Product name: "S-APRO", "U-CAT 18X"

(7) Reactive diluent: “1,2: 8,9 diepoxy limonene”
・ Product name: “Celoxide 3000”, manufactured by Daicel Chemical Industries, Ltd.

(8) Polymerization initiator: Aromatic sulfonium salt-Product name: "San-Aid SI-100L" manufactured by Sanshin Chemical Industry Co., Ltd.

(9) Phosphor (9-1) Phosphor A: “YAG: Ce ³⁺ phosphor” (manufactured by Kasei Optonics Corporation)
(9-2) Phosphor B (phosphorescent phosphor): “SrAl ₂ O ₄ : Eu, Dy phosphor” (manufactured by Nemoto Special Chemical Co., Ltd.)

(10) Silicone resin ・ Product name: “EG6301 (liquid A / liquid B)” manufactured by Toray Dow Corning Co., Ltd.

[Synthesis Example 1]
The resin composition was manufactured by the following process.
(1) Preparation: A circulating water bath was set at 5 ° C. and refluxed to the cooling pipe. Further, an oil bath at 80 ° C. was placed on the magnetic stirrer.
(2) According to the composition ratio shown in Table 1 below, the Bis-A1 epoxy resin, the alkoxysilane compound, and THF are placed in a flask containing a stirrer and mixed and stirred in an atmosphere at 25 ° C. Water and a hydrolysis condensation catalyst were added and mixed and stirred.
(3) Subsequently, a cooling tube was set on the flask, and the flask was immediately immersed in an oil bath at 80 ° C. to start stirring, and reacted for 20 hours while refluxing (refluxing step).
(4) After completion of the reaction, the cooling tube was removed from the flask after cooling to 25 ° C.
(5) The solution after completion of the refluxing process was distilled off at 400 Pa and 50 ° C. for 1 hour using an evaporator, and then further subjected to a dehydration condensation reaction while being distilled off at 80 ° C. for 10 hours (dehydration condensation). Process).
(6) After completion of the dehydration condensation reaction, the mixture was cooled to 25 ° C. to obtain a resin composition.
(7) The above-mentioned mixing indices α1 to ε1 of this resin composition are shown in Table 4 below.
(8) Furthermore, according to the above-mentioned method, the epoxy equivalent (WPE), the starting viscosity and the storage viscosity of the resin composition obtained in the above (6) were measured. Further, the storage stability index θ1 was obtained and shown in Table 4.
The resin composition of Synthesis Example 3 had an epoxy equivalent (WPE) = 242 g / eq, and showed an appropriate value. Further, the starting viscosity = 14.5 Pa · s <1000 Pa · s and the storage viscosity = 16.2 Pa · s <1000 Pa · s, both were fluid liquids. Further, the storage stability index θ3 = 1.12 ≦ 4, and it was found that the resin composition had storage stability.

[Synthesis Example 2]
Resin compositions were produced according to Tables 1 and 2 in the same manner as in Synthesis Example 1, except that the refluxing step was 6 hours. Table 4 shows the results of evaluation by the same method as in Synthesis Example 1, the mixing indices α2 to ε2, and the storage stability index θ2.
As shown in Table 3, the resin composition of Synthesis Example 2 was epoxy equivalent (WPE) = 158 g / eq, and showed an appropriate value. In addition, the starting viscosity = 1.8 Pa · s <1000 Pa · s and the storage viscosity = 3.1 Pa · s <1000 Pa · s, both were fluid liquids. Further, the storage stability index θ2 = 1.72 ≦ 4, and it was found that the resin composition had storage stability.

[Example 1]
A cured product was produced using the resin composition of Synthesis Example 1 stored at 25 ° C. for 2 weeks, and a light resistance test was performed. The results are shown in Table 3.
(1) The above-mentioned resin composition, curing agent and curing accelerator were mixed and stirred in a 25 ° C. atmosphere according to the composition ratios in Table 2, and degassed under vacuum to obtain a cured product solution.
(2) A 3 mm thick, U-shaped silicon rubber was sandwiched between two stainless steel plates coated with a release agent to prepare a molding jig.
(3) The above-mentioned solution for cured product was poured into this molding jig and subjected to curing treatment at 120 ° C. for 1 hour and further at 150 ° C. for 1 hour to produce a cured product.
(4) After the oven internal temperature fell to 30 ° C. or lower, the cured product was taken out, and a sample for light resistance test was prepared according to the method described above.
(5) Table 4 shows the results of the light resistance test conducted by the above-described method using the sample. YI = 10.1 ≦ 13, which is an index of the light resistance test of the cured product, and the light resistance was judged to be acceptable.
(6) Next, 90% by mass of the resin composition of Synthesis Example 1 was mixed with 10% by mass of phosphor A, mixed and stirred for 10 minutes with a planetary mixer (manufactured by Inoue Seisakusho Co., Ltd.), and then under vacuum The defoamed product was used as a fluorescent resin composition.
(7) The fluorescent resin composition was poured into a 50 mL sample bottle and stored at 25 ° C. for 5 hours.
(8) After storage, the side and bottom surfaces were visually confirmed. As a result, there was no precipitation, the phosphor was uniformly dispersed, and the dispersion stability of the fluorescent resin composition was judged to be acceptable. The evaluation results are shown in Table 4.
Furthermore, using the fluorescent resin composition stored at 25 ° C. for 2 weeks, a shell-type LED was manufactured according to the following procedure, and reliability tests (1) to (3) were performed. The results are shown in Table 4.
This bullet-type LED has two lead frames, and a cup portion for mounting an LED chip is formed on one upper end of the lead frame.
(9) Furthermore, the fluorescent resin composition, the curing agent, and the curing accelerator were mixed and stirred according to the composition ratio in Table 3, and degassed under vacuum to obtain an LED sealing material.
(10) The LED sealing material (9) was injected into the cup portion of a bullet-shaped mold frame having a diameter of 5 mm.
(11) An LED chip having an emission wavelength of 400 nm was die-bonded with a silver paste, and a lead frame connected with a bonding wire (copper wire) was immersed therein.
(12) After defoaming in vacuum, curing treatment was performed at 90 ° C. for 1 hour and further at 110 ° C. for 5 hours.
(13) Further, as the outer layer resin, 46.6% by mass of a curing agent and 0.2% by mass of a curing accelerator are added to 53.2% by mass of Bis-A epoxy resin, and the mixture is stirred and mixed. What was deaerated in was poured into a mold frame and cured at 130 ° C. for 1 hour and further at 150 ° C. for 6 hours to obtain a bullet-type LED. The evaluation results are shown in Table 4.
As a result of performing the above “luminescent test”, the reference LED of Comparative Example 1 emitted blue light, whereas the LED of Example 1 emitted white light and was judged to be acceptable.
As a result of performing the above-mentioned “reliability test (1) (L test)”, the minimum value of all LEDs was a total luminous flux maintenance factor (%) = 94% ≧ 90%, and was judged to be acceptable.
Next, as a result of performing the above-mentioned “reliability test (2) (TS test)”, even after 100 cycles of thermal shock, all the LEDs were turned on, and it was judged as passing.
Furthermore, as a result of performing the above-mentioned “reliability test (3) (TC test)”, even after 100 temperature cycles were applied, all the LEDs were lit, and it was judged as passing.
From the above results, the fluorescent resin composition of Example 1 passed all of the dispersion stability test, the light resistance test, the light emission test, and the reliability tests (1) to (3). Judged to pass.

[Example 2]
Using the resin composition of Synthesis Example 2 in place of the resin composition of Synthesis Example 1, the curing treatment temperatures of (3) and (12) of Example 1 were set at 110 ° C. for 4 hours and further at 150 ° C. Table 4 shows the results of producing and evaluating a resin composition, a cured product, a fluorescent resin composition, and an LED according to Tables 1 to 3 in the same manner as in Example 1 except that the time was changed to 1 hour. .
YI = 6.8 ≦ 13, which is an index of light resistance test, and light resistance was judged to be acceptable.
Moreover, the fluorescent resin composition preserve | saved at 25 degreeC for 5 hours did not have precipitation, the fluorescent substance was disperse | distributing uniformly, and the dispersion stability was judged to be a pass.
Next, as a result of performing a “light emission test” of the LED, it was judged that the light was white and passed.
Furthermore, as a result of performing the “reliability test (1) (L test)”, the lowest value of all the LEDs was determined to be acceptable because the total luminous flux maintenance factor (%) = 95% ≧ 90%.
Next, as a result of performing the above-mentioned “reliability test (2) (TS test)”, even after 100 cycles of thermal shock, all the LEDs were turned on, and it was judged as passing.
Subsequently, as a result of performing the above-mentioned “reliability test (3) (TC test)”, all the LEDs were lit even after 100 temperature cycles were applied, and it was judged as passing.
From the above results, the fluorescent resin composition of Example 2 passed all of the dispersion stability test, the light resistance test, the light emission test, and the reliability tests (1) to (3). Judged to pass.

[Example 3]
A phosphor resin composition was prepared and evaluated by blending 60% by mass of the phosphor B with 60% by mass of the resin composition of Synthesis Example 2 in the same manner as in Example 1. When the dispersion stability test of the fluorescent resin composition of Example 3 was carried out, no precipitation was seen, and it was uniform and judged to be acceptable.
Then, the fluorescent resin composition, the reaction diluent and the polymerization initiator are mixed at the ratio shown in Table 5, defoamed under vacuum, and further, in the air, at an air temperature of 23 ° C. and a humidity of 55% RH. Under the conditions, a phosphorescent material (coating film) was produced.
(1) A slide glass having a size of 5 cm × 5 cm was prepared, and the surface was wiped dry with ethanol (Wako Pure Chemical Industries, Ltd., 99.5%).
(2) The fluorescent resin composition was applied onto the slide glass using a bar coater (# 3).
(3) The slide glass was cured at 140 ° C. for 10 minutes to form a coating film.
When the afterglow time was measured by the above-mentioned method as a luminous test of the phosphorescent material (coating film), it was 600 minutes or more, and it was judged to be acceptable.
From the above results, the fluorescent resin composition of Example 3 passed the dispersion stability test and the light emission test, and was judged to be acceptable as a comprehensive judgment. The results are shown in Table 6.
[Reference example]
Using the resin composition of Synthesis Example 1 instead of the fluorescent resin composition of Example 1, a resin composition, a cured product, and an LED were prepared according to Tables 1 to 3, and the evaluation results are shown in Table 4. .
YI = 7.5 ≦ 13, which is an index of the light resistance test, and the light resistance was judged to be acceptable.
Next, as a result of performing the “light emission test” of the LED, it was judged that the light emission was blue and the light emission was unacceptable.
Furthermore, as a result of performing the “reliability test (1) (L test)”, the lowest value of all the LEDs was determined to be acceptable because the total luminous flux maintenance factor (%) = 95% ≧ 90%.
Next, as a result of performing the above-mentioned “reliability test (2) (TS test)”, even after 100 cycles of thermal shock, all the LEDs were turned on, and it was judged as passing.
Subsequently, as a result of performing the above-mentioned “reliability test (3) (TC test)”, all the LEDs were lit even after 100 temperature cycles were applied, and it was judged as passing.

[Comparative Example 1]
Table 4 shows the results of producing and evaluating a fluorescent resin composition using an alicyclic epoxy resin instead of the resin composition of Synthesis Example 1.
When the fluorescent resin composition of Comparative Example 1 was stored at 25 ° C. for 5 hours, the phosphor was precipitated, was non-uniform, and the dispersion stability was judged to be unacceptable. And since the normal fluorescent resin composition was not able to be produced, preparation and evaluation of hardened | cured material and LED were not performed but the comprehensive judgment was judged to be disqualified.

[Comparative Example 2]
A resin composition, a cured product, a fluorescent resin composition, and an LED according to Tables 1 to 3 in the same manner as in Example 1 using a Bis-A epoxy resin instead of the resin composition of Synthesis Example 1. Table 4 shows the results of the fabrication and evaluation.
YI = 17.2> 13, which is an index of the light resistance test, and the light resistance was judged to be unacceptable.
Moreover, the fluorescent resin composition preserve | saved at 25 degreeC for 5 hours did not have precipitation, the fluorescent substance was disperse | distributing uniformly, and the dispersion stability was judged to be a pass.
Next, as a result of performing a “light emission test” of the LED, it was judged that the light was white and passed.
Furthermore, as a result of performing the “reliability test (1) (L test)”, the lowest value of all the LEDs was determined that the total luminous flux maintenance rate (%) = 97% ≧ 90%, which was acceptable.
Next, as a result of performing the above-mentioned “reliability test (2) (TS test)”, even after 100 cycles of thermal shock, all the LEDs were turned on, and it was judged as passing.
Subsequently, as a result of performing the above-mentioned “reliability test (3) (TC test)”, all the LEDs were lit even after 100 temperature cycles were applied, and it was judged as passing.
From the above results, the fluorescent resin composition of Comparative Example 2 passed all of the dispersion stability test, the light emission test, and the reliability tests (1) to (3), but the light resistance was poor. , It was judged as unacceptable as a comprehensive judgment.

[Comparative Example 3]
Instead of the resin composition of Synthesis Example 1, the above-mentioned silicone resin in which the liquid A and the liquid B were mixed and stirred at a mass ratio of 1: 1 was used. Resin composition according to Tables 1 to 3 in the same manner as in Example 1 except that the curing treatment temperature of the cured product and the LED encapsulant was changed to 70 ° C. for 1 hour and further to 150 ° C. for 5 hours. Table 4 shows the results of producing and evaluating cured products, fluorescent resin compositions, and LEDs.
YI = 2.0 ≦ 13, which is an index of the light resistance test, and the light resistance was judged to be acceptable.
Next, as a result of performing a “light emission test” of the LED, it was judged that the light was white and passed.
As a result of performing the above-mentioned “reliability test (1) (L test)”, 3/10 LEDs were not turned on, and the total luminous flux maintenance rate (%) was not measurable, and was judged to be unacceptable.
Next, as a result of performing the above-mentioned “reliability test (2) (TS test)”, after 100 cycles of thermal shock, only 4/10 of the LEDs were turned on, and it was judged as rejected.
Furthermore, as a result of performing the above-mentioned “reliability test (3) (TC test)”, after applying a temperature cycle of 100 cycles, only 6/10 LEDs were turned on, and it was judged as unacceptable.
From the above results, although the fluorescent resin composition of Comparative Example 3 passed the dispersion stability test, the light resistance test, and the light emission test, the results of the reliability tests (1) to (3) were unsatisfactory. It was determined to be acceptable and rejected as a comprehensive judgment.

[Comparative Example 4]
Except for using an alicyclic epoxy resin instead of the resin composition of Synthesis Example 2, a fluorescent resin composition and a phosphorescent material (coating film) were produced in the same manner as in Example 3 according to the formulation in Table 5, A dispersion stability test and a luminescence test were performed. The results are shown in Table 6.
When the dispersion stability test of the fluorescent resin composition of Comparative Example 4 was performed, precipitation occurred, it was uneven, and it was judged as rejected.
When the afterglow time was measured by the above-mentioned method as a luminous test of the phosphorescent material (coating film), it was 600 minutes or more, and it was judged to be acceptable.
From the above results, although the fluorescent resin composition of Comparative Example 4 passed the light emission test, it was determined that the dispersion stability was rejected and rejected as a comprehensive judgment.

The fluorescent resin compositions of Examples 1 and 2 were excellent in dispersion stability, and the cured product was excellent in light resistance. Moreover, the LED using the fluorescent resin composition of Examples 1 and 2 as a sealing material had a good light emission test and an excellent reliability test. Moreover, the fluorescent resin composition of Example 3 was excellent in dispersion stability, and the phosphorescent material had a good light emission test. On the other hand, Comparative Examples 1 and 4 were poor in dispersion stability of the fluorescent resin composition. And at least any one of the light resistance at the time of setting it as hardened | cured material and the light emission test of LED used as a sealing material and a reliability test was unsatisfactory.
As described above, according to the present example, the fluorescent resin composition of the present embodiment is excellent in dispersion stability, the sealing material using it is excellent in reliability, and the phosphorescent material is excellent in light-emitting property. It was shown that

  The fluorescent resin composition of the present embodiment can be used as, for example, a sealing material for LEDs, and is used for backlights for mobile phones, optical disk device heads, LCD backlights, lighting fixtures, automotive lamps and display parts, and traffic signal lamps. It can be used as a lamp, LED display board, outdoor signboard, outdoor display, medical LED, amusement device LED, sealant for general display portions of copy / facsimile and home appliances, and the like. In addition, phosphorescent materials and indications during nighttime and power outages, disaster prevention / safety signs, clocks, wallpaper, electrical switches, signs, clothing, shoes, bicycles / bikes, reflectors, adhesive tapes, fishing hooks / floats Industrial applicability as fishing gear such as sports equipment, sports equipment, accessories, toys, etc.

Claims (9)

(A) an epoxy resin;
An alkoxysilane compound represented by the following general formula (1):
A resin composition obtained by cohydrolyzing and condensing

(In the formula (1), n = 0 to 3, and R ¹ represents a hydrogen atom or an organic group. The plurality of R ² may be the same or different, and may be a hydrogen atom or a carbon number of 1 to 8. Represents an alkyl group of
The alkoxysilane compound is
(B) n = 1-2, and as R ¹ , at least one alkoxysilane compound having at least one cyclic ether group;
(C) at least one alkoxysilane compound in which n = 1 to 2 and R ¹ has at least one aryl group;
A blending index α of (B) and (C) represented by the following formula (2) is 0.001 to 19, and a resin composition:
A phosphor,
A fluorescent resin composition comprising:
Mixing index α = (αc) / (αb) (2)
(In formula (2), αb: content (mol%) of the component (B), αc: content (mol%) of the component (C)).   The fluorescent resin composition according to claim 1, wherein the epoxy resin (A) is a liquid having an epoxy equivalent (WPE) of 100 to 600 g / eq and a viscosity at 25 ° C. of 1000 Pa · s or less.   The fluorescent resin composition according to claim 1 or 2, wherein the (A) epoxy resin is a polyfunctional epoxy resin that is a glycidyl etherified product of a polyphenol compound. As the alkoxysilane compound,
(D) The fluorescent resin composition according to any one of claims 1 to 3, further comprising at least one alkoxysilane compound in which n = 0 in the general formula (1). The fluorescent resin composition according to any one of claims 1 to 4, wherein a mixing index β of the alkoxysilane compound represented by the following formula (3) is 0.01 to 1.4;
Mixing index β = {(β ⁿ² ) / (β ⁿ⁰ + β ⁿ¹ )} (3)
(In formula (3),
β ⁿ² : content (mol%) of the alkoxysilane compound in which n = 2 in the general formula (1),
β ⁿ⁰ : the content (mol%) of the alkoxysilane compound in which n = 0 in the general formula (1),
β ⁿ¹ : content (mol%) of the alkoxysilane compound in which n = 1 in the general formula (1),
Here, 0 ≦ {(β ⁿ⁰ ) / (β ⁿ⁰ + β ⁿ¹ + β ⁿ² )} ≦ 0.1). The fluorescence according to any one of claims 1 to 5, wherein a mixing index γ of the (A) epoxy resin and the alkoxysilane compound represented by the following formula (4) is 0.02 to 15. Resin composition;
Mixing index γ = (γa) / (γs) (4)
(In formula (4),
γa: mass of epoxy resin (g),
γs: mass (g) of alkoxysilane compound in which n = 0 to 2 in the general formula (1)   The fluorescent resin composition according to any one of claims 1 to 6, wherein the phosphor is a yttrium aluminate phosphor (YAG: Ce phosphor) activated with cerium.   The sealing material containing the fluorescent resin composition as described in any one of Claims 1-7.   The luminous material containing the fluorescent resin composition as described in any one of Claims 1-8 whose said fluorescent substance is luminous fluorescent substance.